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We report on the effect of sp3 hybridized carbon atoms in acene derivativesadsorbed on metal surfaces, namely decoupling the molecules from the supportingsubstrates. In particular, we have used a Ag(100) substrate and hydrogenatedheptacene molecules, in which the longest conjugated segment determining itsfrontier molecular orbitals amounts to five consecutive rings. Thenon-planarity that the sp3 atoms impose on the carbon backbone results inelectronically decoupled molecules, as demonstrated by the presence of chargingresonances in dI/dV tunneling spectra and the associated double tunnelingbarriers, or in the Kondo peak that is due to a net spin S=1/2 of the moleculeas its LUMO becomes singly charged. The spatially dependent appearance of thecharging resonances as peaks or dips in the differential conductance spectra isfurther understood in terms of the tunneling barrier variation upon molecularcharging, as well as of the different orbitals involved in the tunnelingprocess.

Electronic Decoupling of Polyacenes from the Underlying Metal Substrate by sp3 Carbon Atoms